High-wear-resistance aliphatic isocyanate and preparation method thereof

Abstract

The invention relates to high-wear-resistance aliphatic isocyanate and a preparation method thereof, and belongs to the technical field of isocyanate synthesis. 2-methyl-1, 5-pentamethylene diamine is converted into self-made aliphatic isocyanate with steric hindrance through a triphosgene method, sliding of a polyurethane molecular chain is limited, and wear resistance is improved. And compounding with modified nano calcium carbonate treated by a coupling agent to obtain the high-wear-resistance aliphatic isocyanate. And the modified nano calcium carbonate improves the compatibility, avoids agglomeration, enhances interface bonding and further improves the wear resistance. The aliphatic isocyanate prepared by the preparation method disclosed by the invention has a remarkable high wear-resistant effect.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of isocyanate synthesis, in particular to a high-wear-resistance aliphatic isocyanate and a preparation method thereof. BACKGROUND

[0002] As a core raw material for preparing polyurethane materials, aliphatic isocyanate is widely used in fields such as coatings, adhesives and elastomers which have clear requirements for wear resistance, and the performance of the aliphatic isocyanate directly determines the service life and application scenarios of downstream polyurethane products.

[0003] In the current industry, the conventional aliphatic isocyanate is difficult to meet the high-load use requirements due to the strong sliding property of the polyurethane molecular chain formed by the reaction of the aliphatic isocyanate with polyols because the molecular structure of the aliphatic isocyanate lacks steric hindering groups; although there are studies on improving the wear resistance by adding inorganic fillers such as nano calcium carbonate, the nano calcium carbonate which is not modified or insufficiently modified is prone to agglomeration, has poor compatibility with the isocyanate matrix, cannot play a reinforcing role, and may even introduce performance defects due to the existence of the agglomerates, thereby affecting the overall wear resistance. SUMMARY

[0004] The application aims to provide a high-wear-resistance aliphatic isocyanate and a preparation method thereof to solve the problems in the prior art.

[0005] In order to solve the above technical problems, the application provides the following technical scheme: a high-wear-resistance aliphatic isocyanate comprises the following steps: (1) under a nitrogen atmosphere, triphosgene and toluene are mixed at a mass ratio of 1-2:4-6, stirred at room temperature for 30 min to form a reaction liquid; 2-methyl-1,5-pentanediamine and toluene are mixed at a mass ratio of 3-5:4-6, stirred at room temperature for 30 min to form a dropwise liquid; the reaction liquid is placed in an ice water bath, the temperature is kept at 0-5 DEG C, and the dropwise liquid with a mass of 0.4-0.6 times that of the reaction liquid is slowly added while stirring; after the dropwise addition is completed, the temperature is slowly increased to 80 DEG C, and reflux reaction is carried out for 3-4 h until no obvious HCl gas is generated; the temperature is naturally cooled to room temperature, and the target fraction is collected after filtration, rotary evaporation and vacuum distillation to obtain a self-made aliphatic isocyanate; (2) under a nitrogen atmosphere, the pretreated nano calcium carbonate and ethanol are mixed at a mass ratio of 1-2:5, heated to 70-80 DEG C and stirred, and the coupling agent hydrolysis liquid with a mass of 1-1.5 times that of the nano calcium carbonate is added dropwise; after the dropwise addition is completed, the stirring is continued for 1-2 h, and the temperature is cooled to room temperature; centrifugation is carried out for 10 min, and the precipitate is dried at 60 DEG C for 4 h to obtain the nano calcium carbonate treated with the coupling agent; (3) under the atmosphere of nitrogen, the nano calcium carbonate treated by coupling agent, the bio-based aliphatic isocyanate and the organic solvent are mixed according to the mass ratio of 1-2:0.1-0.3:5, and after the reaction is stirred at 30℃ for 3-5h, centrifugal separation is carried out for 15min, and the precipitate is dried at 50℃ for 4h to obtain the modified nano calcium carbonate grafted with isocyanate; after the self-made aliphatic isocyanate and the modified nano calcium carbonate are mixed according to the mass ratio of 1-2:0.2-0.5, the high wear-resistant aliphatic isocyanate is obtained by stirring at room temperature for 30min.

[0006] Further, the dropping speed of the dropping liquid in step (1) is 1mL / min.

[0007] Further, the target fraction in step (1) is the fraction of 115-120℃ / 1mmHg.

[0008] Further, the reaction process of the self-made aliphatic isocyanate in step (1) is as follows: .

[0009] Further, the particle size of the nano calcium carbonate in step (2) is 20nm.

[0010] Further, the coupling agent in step (2) is KH-550.

[0011] Further, the dropping speed of the coupling agent hydrolysate in step (2) is 2mL / min.

[0012] Further, the bio-based aliphatic isocyanate in step (3) is bio-based 1,5-pentylene diisocyanate obtained by the photochlorination reaction of 1,5-pentylene diamine, which is obtained by fermentation of 1,5-pentylene diamine through the action of biological enzyme with glucose as the biological raw material.

[0013] Further, the organic solvent in step (3) is dichloromethane.

[0014] Further, the application of the high wear-resistant aliphatic isocyanate is characterized in that 4-6 parts by weight of polyol are heated to 100℃, vacuum dehydration is carried out for 1h, and then the temperature is lowered to 50℃; 1-2 parts by weight of the high wear-resistant aliphatic isocyanate, 0.1 part by weight of catalyst and 10 parts by weight of toluene are added, the reaction is stirred at 90℃ for 3h, then 0.2 part by weight of chain extender is added, the reaction is continuously stirred at 90℃ for 2h, and finally the product is discharged after cooling to 30℃ to obtain a polyurethane material.

[0015] Further, the polyol is polybutylene adipate with a molecular weight of 2000.

[0016] Further, the catalyst is dibutyltin dilaurate.

[0017] Further, the chain extender is 1,4-butanediol.

[0018] Compared with the prior art, the application has the following beneficial effects: The application compounding self-made aliphatic isocyanate with modified nanofiller to achieve high wear resistance.

[0019] The application first converts 2-methyl-1,5-pentanediamine into self-made aliphatic isocyanate by the method of triphosgene. The methyl branch will produce steric hindrance, limiting the sliding ability of the polyurethane molecular chain formed by the reaction of isocyanate and polyol, and the straight-chain structure of the main chain makes it easy to form a regular crystalline region in subsequent applications, thereby improving the overall wear resistance. After compounding with modified nanometer calcium carbonate treated by coupling agent and grafted with isocyanate, high wear resistance aliphatic isocyanate is obtained. On the one hand, the compatibility of the modified nanometer calcium carbonate is greatly improved, avoiding the wear defects caused by agglomeration, and on the other hand, after compounding, it will bond with polyol in subsequent applications, enhance the interface bonding, so that the inorganic reinforcing phase can further improve the overall wear resistance. Low-toxicity process and low-cost raw materials make high wear resistance aliphatic isocyanate have good environmental protection and economy. DETAILED DESCRIPTION

[0020] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the embodiments of the application. Obviously, the described embodiments are only a part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the application.

[0021] In order to more clearly illustrate the method provided by the application, the following embodiments are used for detailed description. In the following embodiments, the test methods of various indexes of high wear resistance aliphatic isocyanate prepared are as follows: Wear resistance test: the polyurethane material prepared in examples 1-3 and comparative examples 1-6 is made into a sample coating and placed on a paper tape wear tester, a 175g force is vertically rubbed, 1000 test cycles are set, the appearance is observed at 300 cycles, and the sample surface coating is observed with a 60 times light magnifying glass every 50 cycles after 300 cycles. The maximum number of cycles when the coating is worn out is recorded. If the coating is observed to be worn out at 450 cycles, the cycle number is recorded as 400 cycles.

[0022] Weather resistance test: after being placed in an environment of 80 DEG C and 75% humidity for 1000 hours, the tensile strength and elongation at break of the resin film formed by the polyurethane material in examples 1-5 and comparative examples 1-6 are tested.

[0023] Example 1 (1) Under nitrogen atmosphere, mixed triphosgene and toluene with mass ratio of 1:4, stirred at room temperature with speed of 300 rpm for 30 min to form reaction liquid; mixed 2-methyl-1,5-pentanediamine and toluene with mass ratio of 3:4, stirred at room temperature with speed of 300 rpm for 30 min to form dropping liquid; placed the reaction liquid in ice water bath, kept the temperature at 0℃, and slowly added the dropping liquid with 0.4 times of the mass of the reaction liquid at speed of 800 rpm, the dropping rate was 1 mL / min, after the dropping was completed, removed the ice water bath, and slowly heated the reaction liquid to 80℃ at a rate of 2℃ / min, refluxed for 3h, during which time, checked with moistened pH paper at the outlet of the condenser tube until no obvious HCl gas was generated, naturally cooled to room temperature, filtered and evaporated the filtrate by rotary evaporator at 60℃, vacuum degree-0.1 kPa for 1h, then vacuum distilled, collected the fraction at 115℃ / 1mmHg to obtain self-made aliphatic isocyanate; (2) Placed 20g of calcium carbonate with particle size of 20nm in a forced air drying oven, dried at 105℃ for 4h to remove physically adsorbed water, and cooled to be ready for use; mixed ethanol and water with mass ratio of 9:1 to prepare an ethanol solution; while stirring the ethanol solution at a speed of 100 rpm, added KH-550 silane coupling agent dropwise, the dropping rate was 1 mL / min, and after the added silane coupling agent was fully dissolved, added more to prevent incomplete reaction and form a precipitate; adjusted the pH value of the mixed solution to 2.0 by adding 1M HNO3 dropwise, and then heated the mixed solution to 90℃ by a reflux device, and let the solution react at 90℃ for 20 min to obtain a silane coupling agent hydrolysis solution; under nitrogen atmosphere, mixed the dried nano calcium carbonate and ethanol with mass ratio of 1:5, heated to 70℃, stirred at a speed of 1000 rpm, and at the same time, added the coupling agent hydrolysis solution with 1 times the mass of the nano calcium carbonate, the dropping rate was 2 mL / min, after the dropping was completed, continued to stir for 1h, cooled to room temperature, and centrifuged at a speed of 6000 rpm for 10 min, placed the precipitate in a 60℃ drying oven for 4h to obtain nano calcium carbonate treated with a coupling agent; (3) Under nitrogen atmosphere, mixed the nano calcium carbonate treated with a coupling agent, 1,5-pentanediamine obtained by fermentation of glucose as a biological raw material by the action of a biological enzyme, bio-based 1,5-pentanediamine isocyanate prepared from 1,5-pentanediamine by phosgenation reaction, and dichloromethane with mass ratio of 1:0.1:5, heated to 30℃, stirred at a speed of 500 rpm for 3h, centrifuged at a speed of 5000 rpm for 15 min, and dried the precipitate at 50℃ for 4h to obtain modified nano calcium carbonate grafted with isocyanate; (4) The self-made aliphatic isocyanate and modified nano calcium carbonate were mixed in a mass ratio of 1:0.2, and then stirred at room temperature at a speed of 500 rpm for 30 min to obtain high wear-resistant aliphatic isocyanate; 4 parts by weight of polyol were heated to 100°C, vacuum dehydrated for 1 h, and then cooled to 50°C; 1 part by weight of high wear-resistant aliphatic isocyanate, 0.1 part by weight of catalyst and 10 parts by weight of toluene were added, and the reaction was stirred at a speed of 500 rpm for 3 h after being heated to 90°C, then 0.2 parts by weight of chain extender were added, and the reaction was continued to stir at 90°C for 2 h, and finally the product was discharged after being cooled to 30°C to obtain polyurethane material.

[0024] Example 2 (1) Under a nitrogen atmosphere, carbonyldimidazole and toluene were mixed in a mass ratio of 1.5:5, stirred at room temperature at a speed of 300 rpm for 30 min to form a reaction solution; 2-methyl-1,5-pentanediamine and toluene were mixed in a mass ratio of 4:5, stirred at room temperature at a speed of 300 rpm for 30 min to form a dropwise solution; the reaction solution was placed in an ice water bath, the temperature was kept at 3°C, and the dropwise solution with 0.5 times the mass of the reaction solution was slowly added at a speed of 800 rpm, the dropwise rate was 1 mL / min, after the addition was completed, the ice water bath was removed, and the reaction solution was slowly heated to 80°C at a speed of 2°C / min, refluxed for 3.5 h, during which the outlet of the condenser tube was checked with moist pH paper until no obvious HCl gas was generated, and then naturally cooled to room temperature, filtered and evaporated at 65°C under vacuum degree-0.1 kPa for 1 h by a rotary evaporator, then vacuum distilled, and the fraction collected at 118°C / 1 mmHg to obtain self-made aliphatic isocyanate; (2) 20 g of calcium carbonate with a particle size of 20 nm was placed in a forced air drying oven and dried at 105°C for 4 h to remove physically adsorbed water, and then cooled for standby; ethanol and water were mixed in a mass ratio of 9:1 to prepare an ethanol solution; while stirring the ethanol solution at a speed of 100 rpm, KH-550 silane coupling agent was added dropwise at a rate of 1 mL / min, and after the added silane coupling agent was fully dissolved, it was added again to prevent incomplete reaction and form a precipitate; the pH value of the mixed solution was adjusted to 2.0 by adding 1M HNO3, and then the mixed solution was heated to 90°C by a reflux device, and the solution was kept at 90°C for 20 min to obtain a silane coupling agent hydrolysis solution; under a nitrogen atmosphere, the dried nano calcium carbonate and ethanol were mixed in a mass ratio of 1.5:5, heated to 75°C, and stirred at a speed of 1000 rpm, while adding the coupling agent hydrolysis solution with 1.3 times the mass of the nano calcium carbonate at a rate of 2 mL / min, and after the addition was completed, the stirring was continued for 1.5 h, and then cooled to room temperature, centrifuged at a speed of 6000 rpm for 10 min, and the precipitate was dried at 60°C for 4 h to obtain nano calcium carbonate treated with a coupling agent; (3) Under the atmosphere of nitrogen, the nano calcium carbonate treated by coupling agent, 1,5-pentanediamine obtained by fermentation of glucose as a biological raw material through the action of biological enzyme, and bio-based 1,5-pentane diisocyanate prepared by phosgenation reaction of 1,5-pentanediamine were mixed in a mass ratio of 1.5:0.2:5, and then the mixture was heated to 30°C and stirred at a speed of 500 rpm for 4 h. After that, the mixture was centrifuged at a speed of 5000 rpm for 15 min, and the precipitate was dried at 50°C for 4 h to obtain the modified nano calcium carbonate grafted with isocyanate; (4) The self-made aliphatic isocyanate and the modified nano calcium carbonate were mixed and compounded in a mass ratio of 1.5:0.35, and then stirred at room temperature and at a speed of 500 rpm for 30 min to obtain the high-wear-resistance aliphatic isocyanate. 5 parts by weight of a polyol were heated to 100°C, and then vacuum dehydrated for 1 h. After that, the temperature was lowered to 50°C, and 1.5 parts by weight of the high-wear-resistance aliphatic isocyanate, 0.1 part by weight of a catalyst, and 10 parts by weight of toluene were added. The mixture was heated to 90°C and stirred at a speed of 500 rpm for 3 h. Then, 0.2 parts by weight of a chain extender was added, and the mixture was continuously stirred at 90°C for 2 h. Finally, the mixture was cooled to 30°C and discharged to obtain a polyurethane material.

[0025] Example 3 (1) Under the atmosphere of nitrogen, triphosgene and toluene were mixed in a mass ratio of 2:6, and then stirred at room temperature and at a speed of 300 rpm for 30 min to form a reaction liquid. 2-methyl-1,5-pentanediamine and toluene were mixed in a mass ratio of 5:6, and then stirred at room temperature and at a speed of 300 rpm for 30 min to form a dropping liquid. The reaction liquid was placed in an ice water bath, and the temperature was kept at 5°C. While stirring at a speed of 800 rpm, the dropping liquid was slowly added at a rate of 1 mL / min. After the addition was completed, the ice water bath was removed, and the reaction liquid was slowly heated to 80°C at a rate of 2°C / min. The reaction was carried out under reflux for 4 h. During the reaction, a wet pH test paper was used to check the outlet of the condenser tube until no obvious HCl gas was generated. The reaction liquid was naturally cooled to room temperature, filtered, and then evaporated at 70°C and under a vacuum degree of -0.1 kPa for 1 h by using a rotary evaporator. Vacuum distillation was carried out, and the fraction collected at 120°C / 1 mmHg was obtained to obtain the self-made aliphatic isocyanate. (2) 20 g of calcium carbonate with a particle size of 20 nm was placed in a forced air drying oven and dried at 105°C for 4 h to remove physically adsorbed water, and then cooled and reserved; ethanol and water were mixed in a mass ratio of 9:1 to prepare an ethanol solution; while stirring the ethanol solution at a speed of 100 rpm, the silane coupling agent KH-550 was added dropwise at a rate of 1 mL / min, and after the added silane coupling agent was fully dissolved, it was added dropwise to prevent insufficient reaction and sedimentation; the pH value of the mixed solution was adjusted to 2.0 by adding 1M HNO3 dropwise, and then the mixed solution was heated to 90°C by a reflux device, and the solution was kept at 90°C for 20 min to obtain a silane coupling agent hydrolyzate; under a nitrogen atmosphere, the dried nano calcium carbonate was mixed with ethanol in a mass ratio of 2:5, heated to 80°C, stirred at a speed of 1000 rpm, and the coupling agent hydrolyzate was added dropwise at a rate of 2 mL / min, and after the addition was completed, stirring was continued for 2 h, and then cooled to room temperature, centrifuged at a speed of 6000 rpm for 10 min, and the precipitate was dried at 60°C for 4 h to obtain nano calcium carbonate treated with a coupling agent; (3) under a nitrogen atmosphere, the nano calcium carbonate treated with a coupling agent, 1,5-pentanediamine obtained by fermentation of glucose as a biological raw material by the action of an enzyme, and bio-based 1,5-pentanediyiisocyanate prepared from 1,5-pentanediamine by a phosgenation reaction were mixed in a mass ratio of 2:0.3:5, heated to 30°C, stirred at a speed of 500 rpm for 5 h, centrifuged at a speed of 5000 rpm for 15 min, and the precipitate was dried at 50°C for 4 h to obtain modified nano calcium carbonate grafted with isocyanate; (4) the self-made aliphatic isocyanate and the modified nano calcium carbonate were mixed in a mass ratio of 2:0.5, and then stirred at a speed of 500 rpm at room temperature for 30 min to obtain a high wear-resistant aliphatic isocyanate; 6 parts by weight of a polyol was heated to 100°C, vacuum dehydrated for 1 h, and then cooled to 50°C; 2 parts by weight of the high wear-resistant aliphatic isocyanate, 0.1 parts by weight of a catalyst, and 10 parts by weight of toluene were added, heated to 90°C, stirred at a speed of 500 rpm for 3 h, then 0.2 parts by weight of a chain extender was added, and the reaction was continued at 90°C for 2 h, and finally cooled to 30°C to obtain a polyurethane material.

[0026] Comparative Example 1 The difference between Comparative Example 1 and Example 2 is that there is no step (1), and step (4) is changed to: first, 5 parts by weight of polyol is warmed to 100°C, vacuum dehydration for 1 h, then cooled to 50°C; 1.5 parts by weight of modified nano calcium carbonate, 0.1 parts by weight of catalyst and 10 parts by weight of toluene are added, warmed to 90°C, stirred at a speed of 500 rpm for 3 h, then 0.2 parts by weight of chain extender is added, and the reaction is continued at 90°C for 2 h, and finally cooled to 30°C to discharge the polyurethane material. The remaining steps are the same as in Example 2.

[0027] Comparative Example 2 The difference between Comparative Example 2 and Example 2 is that there is no step (2), and step (3) is changed to: under a nitrogen atmosphere, 20 nm nano calcium carbonate treated by plasma with a flow rate of 50 sccm of argon-water vapor mixed at a volume ratio of 4:1, 1,5-pentanediamine obtained by fermentation of glucose as a biological raw material by enzyme action, and bio-based 1,5-pentanediamine isocyanate prepared by phosgenation reaction of 1,5-pentanediamine are mixed at a mass ratio of 1.5:0.2:5, warmed to 30°C, stirred at a speed of 500 rpm for 4 h, then centrifuged at 5000 rpm for 15 min, and the precipitate is dried at 50°C for 4 h to obtain modified nano calcium carbonate grafted with isocyanate. The remaining steps are the same as in Example 2.

[0028] Comparative Example 3 The difference between Comparative Example 3 and Example 2 is that there is no step (3), and step (4) is changed to: self-made aliphatic isocyanate and nano calcium carbonate treated by coupling agent are mixed and compounded at a mass ratio of 1.5:0.35 to obtain high wear-resistant aliphatic isocyanate at room temperature with stirring at a speed of 500 rpm for 30 min; first, 5 parts by weight of polyol is warmed to 100°C, vacuum dehydration for 1 h, then cooled to 50°C; 1.5 parts by weight of high wear-resistant aliphatic isocyanate, 0.1 parts by weight of catalyst and 10 parts by weight of toluene are added, warmed to 90°C, stirred at a speed of 500 rpm for 3 h, then 0.2 parts by weight of chain extender is added, and the reaction is continued at 90°C for 2 h, and finally cooled to 30°C to discharge the polyurethane material. The remaining steps are the same as in Example 2.

[0029] Comparative Example 4 The difference between Comparative Example 4 and Example 2 is that steps (2) and (3) are omitted, and step (4) is changed to: first, 5 parts by weight of the polyol is warmed to 100°C, vacuum dehydration for 1 h, and then cooled to 50°C; 1.5 parts by weight of the self-made aliphatic isocyanate, 0.1 parts by weight of the catalyst, and 10 parts by weight of toluene are added, warmed to 90°C, stirred at a speed of 500 rpm for 3 h, then 0.2 parts by weight of the chain extender is added, and the stirring is continued at 90°C for 2 h, and finally cooled to 30°C to discharge the polyurethane material.

[0030] Comparative Example 5 The difference between Comparative Example 5 and Example 2 is that steps (1), (2), and (3) are omitted, and step (4) is changed to: first, 5 parts by weight of the polyol is warmed to 100°C, vacuum dehydration for 1 h, and then cooled to 50°C; 1.5 parts by weight of the bio-based 1,5-pentanediamine isocyanate prepared from 1,5-pentanediamine obtained by fermentation of glucose as a biological raw material through the action of a biological enzyme by a phosgenation reaction, 0.1 parts by weight of the catalyst, and 10 parts by weight of toluene are added, warmed to 90°C, stirred at a speed of 500 rpm for 3 h, then 0.2 parts by weight of the chain extender is added, and the stirring is continued at 90°C for 2 h, and finally cooled to 30°C to discharge the polyurethane material.

[0031] Comparative Example 6 The difference between Comparative Example 6 and Example 2 is that steps (2) and (3) are omitted, and step (4) is changed to: the self-made aliphatic isocyanate and the bio-based 1,5-pentanediamine isocyanate prepared from 1,5-pentanediamine obtained by fermentation of glucose as a biological raw material through the action of a biological enzyme by a phosgenation reaction are mixed in a mass ratio of 1.5:0.35, and high wear-resistant aliphatic isocyanate is obtained by stirring at room temperature at a speed of 500 rpm for 30 min; first, 5 parts by weight of the polyol is warmed to 100°C, vacuum dehydration for 1 h, and then cooled to 50°C; 1.5 parts by weight of the high wear-resistant aliphatic isocyanate, 0.1 parts by weight of the catalyst, and 10 parts by weight of toluene are added, warmed to 90°C, stirred at a speed of 500 rpm for 3 h, then 0.2 parts by weight of the chain extender is added, and the stirring is continued at 90°C for 2 h, and finally cooled to 30°C to discharge the polyurethane material.

[0032] Effect Example The performance analysis results of the high wear-resistant aliphatic isocyanate obtained by using Examples 1 to 3 and Comparative Examples 1 to 6 of the present application are given in Table 1 below.

[0033] Table 1

[0034] From the comparison of the experimental data of wear resistance of the examples and the comparative examples, it can be found that the 2-methyl-1, 5-pentanediamine is firstly converted into the self-made aliphatic isocyanate by the triphosgene method in the present application, the methyl branch of the isocyanate produces steric hindrance, which can limit the sliding of the polyurethane molecular chain formed by subsequent reaction with polyol, so as to improve the wear resistance; then the aliphatic isocyanate with high wear resistance is obtained by compounding the isocyanate with the modified nano calcium carbonate treated by coupling agent and grafted with isocyanate; the modified nano calcium carbonate can not only improve the compatibility to avoid the wear defects caused by agglomeration, but also can be bonded with polyol to enhance the interface bonding, so as to further improve the wear resistance; from the comparison of the experimental data of weather resistance of the examples and the comparative examples, it can be found that the self-made aliphatic isocyanate and the modified nano calcium carbonate are compounded, which further improves the overall weather resistance.

[0035] It will be obvious to a person skilled in the art that the application is not limited to the details of the above-described exemplary embodiments, but that the application can be implemented in other concrete forms without departing from the spirit or essential characteristics of the application. The embodiments should therefore be considered in all respects as illustrative and not restrictive, the scope of the application being defined by the appended claims rather than by the above description, and it is therefore intended that all changes and modifications that fall within the meaning and range of equivalents of the claims be embraced therein. Any reference signs in the claims should not be construed as limiting the claims concerned.

Claims

1. A highly abrasion resistant aliphatic isocyanate characterized in that, Comprise the following steps: (1) Under the atmosphere of nitrogen, triphosgene and toluene are mixed in a mass ratio of 1-2:4-6, stirred at room temperature for 30 min to form a reaction solution; 2-methyl-1, 5-pentanediamine and toluene are mixed in a mass ratio of 3-5:4-6, stirred at room temperature for 30 min to form a dropwise solution; the reaction solution is placed in an ice water bath, the temperature is kept at 0-5℃, and the dropwise solution of 0.4-0.6 times the mass of the reaction solution is slowly added while stirring; after the addition is completed, the temperature is slowly raised to 80℃, and reflux reaction is carried out for 3-4h until no obvious HCl gas is generated; the temperature is naturally cooled to room temperature, filtered, and then rotary evaporated, vacuum distilled to collect the target fraction to obtain self-made aliphatic isocyanate; (2) Under the atmosphere of nitrogen, the pretreated nano calcium carbonate and ethanol are mixed in a mass ratio of 1-2:5, heated to 70-80℃ and stirred, and the hydrolyzate of the coupling agent is added in an amount of 1-1.5 times the mass of the nano calcium carbonate; after the addition is completed, stirring is continued for 1-2h, and then the temperature is cooled to room temperature and centrifuged for 10 min; the precipitate is dried at 60℃ for 4h to obtain nano calcium carbonate treated with the coupling agent; (3) Under the atmosphere of nitrogen, the nano calcium carbonate treated with the coupling agent, the bio-based aliphatic isocyanate and the organic solvent are mixed in a mass ratio of 1-2:0.1-0.3:5, heated to 30℃ and stirred for 3-5h, then centrifuged for 15 min, and the precipitate is dried at 50℃ for 4h to obtain modified nano calcium carbonate grafted with isocyanate; the self-made aliphatic isocyanate and the modified nano calcium carbonate are mixed in a mass ratio of 1-2:0.2-0.5, and then stirred at room temperature for 30 min to obtain high-wear-resistance aliphatic isocyanate.

2. A high abrasion resistant aliphatic isocyanate according to claim 1, characterized in that, The dropwise rate of the dropwise solution in step (1) is 1mL / min.

3. A high abrasion resistant aliphatic isocyanate according to claim 1, characterized in that, The target fraction in step (1) is a fraction at 115-120℃ / 1mmHg.

4. A high abrasion resistant aliphatic isocyanate according to claim 1, characterized in that, The reaction process of the self-made aliphatic isocyanate in step (1) is: 。 5. A high abrasion resistant aliphatic isocyanate according to claim 1, characterized in that, The particle size of the nano calcium carbonate in step (2) is 20nm.

6. A high abrasion resistant aliphatic isocyanate according to claim 1, characterized in that, The coupling agent in step (2) is KH-550.

7. A high abrasion resistant aliphatic isocyanate according to claim 1, characterized in that, The dropwise rate of the hydrolyzate of the coupling agent in step (2) is 2mL / min.

8. A high abrasion resistant aliphatic isocyanate according to claim 1, characterized in that, The bio-based aliphatic isocyanate in step (3) is bio-based 1, 5-pentanediamine isocyanate prepared from 1, 5-pentanediamine obtained by fermentation of glucose as a biological raw material through the action of a biological enzyme through a phosgenation reaction.

9. A high abrasion resistant aliphatic isocyanate according to claim 1, characterized in that, The organic solvent in step (3) is dichloromethane.

10. Use of a highly abrasion resistant aliphatic isocyanate characterized in that, First, 4-6 parts by weight of a polyol are heated to 100℃, vacuum dehydrated for 1h, and then cooled to 50℃; 1-2 parts by weight of high-wear-resistance aliphatic isocyanate, 0.1 parts by weight of a catalyst and 10 parts by weight of toluene are added, heated to 90℃ and stirred for 3h, then 0.2 parts by weight of a chain extender is added, and the temperature is kept at 90℃ for 2h of further stirring; finally, the temperature is cooled to 30℃ and the product is discharged to obtain a polyurethane material.

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